US6130260A - Method for converting natural gas to liquid hydrocarbons - Google Patents
Method for converting natural gas to liquid hydrocarbons Download PDFInfo
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- US6130260A US6130260A US09/199,502 US19950298A US6130260A US 6130260 A US6130260 A US 6130260A US 19950298 A US19950298 A US 19950298A US 6130260 A US6130260 A US 6130260A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
- B01J12/002—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor carried out in the plasma state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0881—Two or more materials
- B01J2219/0883—Gas-gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0894—Processes carried out in the presence of a plasma
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Definitions
- This invention pertains to conversion of natural gas to liquid hydrocarbons. More particularly, methane is converted to reactive hydrocarbons and the reactive hydrocarbons are reacted with additional methane to form liquid hydrocarbons.
- Natural gas often contains about 90 mole per cent methane mixed with heavier alkanes. Alkanes of increasing carbon number are normally present in decreasing amounts. Carbon dioxide and other gases may be present.
- U.S. Pat. No. 5,277,773 discloses a conversion process that subjects the methane plus hydrocarbons to microwave radiation so as to produce an electric discharge in an electromagnetic field.
- U.S. Pat. No. 5,131,993 discloses a method for cracking a hydrocarbon material in the presence of a microwave discharge plasma and a carrier gas, such as oxygen, hydrogen and nitrogen, and, generally, a catalyst.
- U.S. Pat. No. 3,389,189 is an example of patents relating to production of acetylene by an electric arc.
- Methane pyrolysis to acetylene and hydrogen by rapid heating in a reaction zone and subsequent rapid quenching has also been extensively investigated.
- Subatmospheric pressures and specific ranges of velocities of hydrocarbon gases through the reaction zone are disclosed in U.S. Pat. No. 3,156,733. Heat is supplied by burning of hydrocarbons.
- FIG. 1 shows a process diagram for one embodiment of the process of this invention in which the natural gas is heated to reaction temperature by burning of hydrogen in a furnace.
- FIG. 2 shows a process diagram of another embodiment of the process of this invention in which the natural gas is heated to reaction temperature by electrical energy produced by hydrogen.
- FIG. 3 shows a graph of equilibrium values of moles of species formed from one mole of methane as a function of temperature of reaction at a pressure of 10 bars.
- a process for conversion of natural gas to a liquid for transport from remote locations is provided.
- the natural gas is heated to a temperature at which a fraction of the methane is converted to hydrogen and a reactive hydrocarbon such as acetylene, the stream is quenched to stop further reactions, and the stream is then reacted in the presence of a catalyst to form the liquid to be transported, predominantly pentane.
- Hydrogen may be separated after quenching and before the catalytic reactor.
- Heat for raising the temperature of the natural gas stream is provided by burning of hydrogen under conditions to produce a preferred range of temperature in a furnace.
- the hydrogen produced in the process is used to generate electrical power and the electrical power is used to heat the natural gas stream.
- the range of temperature to which the natural gas is heated is from about 1600 to about 2500 K and preferably from about 1600 to about 1800 K. Pressure is preferably in the range from about 10 bars to about 50 bars. Little or none of the incoming natural gas is burned for fuel.
- FIG. 1 shows a preferred embodiment of the steps for producing reactive gas such as acetylene from natural gas in the present invention.
- hydrogen derived from the high temperature reactor and separated from the reactive hydrocarbon e.g., acetylene
- the reactive hydrocarbon e.g., acetylene
- Flame temperature of hydrogen is adequate to reach a desired reaction temperature without oxygen enrichment of air, but sufficient enrichment can be easily achieved with membrane units, which are well known in the art, and this will avoid the necessity of NOx control in emissions from the furnace.
- Addition of water to the combustion zone of the furnace may be used to lower flame temperature to a desired range, preferably about 300 to 500 K above the preferred reaction temperature of natural gas passing through tubes in the furnace.
- Residence time of gas in the tubes should be long enough to convert the natural gas to acetylene and other reactive compounds and not so long as to allow significant further reactions before the quenching step, which is discussed below.
- the hydrocarbon products of the reactions are designated herein as "reactive products.”
- the energy required to drive the reactions at a temperature of 2500 K is shown in Table 1, as calculated from data in the TRC Thermodynamic Tables--Hydrocarbons (available from the Thermodynamics Research Center, Texas A & M University, College Station, Tex.). Mole fractions of methane, acetylene, ethylene, hydrogen molecules and atomic hydrogen are shown for pressures of one bar, 10 bars and 50 bars. Number of moles of each material is also shown in the table. Note that energy requirements ( ⁇ H) are slightly decreased at higher pressures and the conversion efficiency of methane to acetylene is very high.
- the amount of atomic hydrogen produced is significantly less at pressures above 1 bar. If the moles of hydrogen produced are reacted with oxygen the enthalpy change is calculated to be 850 kJ, as shown at the bottom of the table, which is significantly more than the enthalpy required in the reaction. If the hydrogen can be utilized in a process operating at about 80% thermal efficiency, using two preheaters 14 and 15 in FIG. 1, these calculations show that the process to convert methane to acetylene can be operated at energy self-sufficient conditions at 2500 K, i.e., all the energy is derived from burning of the hydrogen that is a product of the reaction.
- Rapid cooling or "quenching” is essential, in a time on-the-order-of 10-100 milliseconds.
- This quench may be achieved by "dumping" the reaction products into water, or, alternatively, the natural gas feed or the liquid products may be used in the quench, which may occur in vessel 11.
- Hydrogen may then be separated from any liquid present in separator 12 and fed to furnace 10.
- the reactive hydrocarbon (mostly acetylene) is then directed to low-temperature catalytic liquefaction reactor 13.
- Incoming natural gas is preferably pre-heated in pre-heaters 14 and 15 before it is heated to the preferred reaction temperature by heat exchange with the hydrogen-combustion gas. Water is separated from the combustion gas in separator 16. Flue gas from the hydrogen furnace, water (that may be considered a product in some plant locations) and liquid hydrocarbon product are discharged from the process.
- the preferred reaction temperature is in the range from about 1600 to about 2500 K.
- the hydrogen and acetylene or other reactive hydrocarbons are separated, with the evolved hydrogen going directly to the hydrogen furnace and the reactive hydrocarbon bottoms going to a liquefaction reactor.
- hydrogen is directed to catalytic reactor 13 without the separation step of separator 12.
- the high temperature water vapor (steam) from hydrogen combustion is passed through a shell outside tubes carrying natural gas in a heat exchanger to raise the temperature of the natural gas to the selected reaction temperature and condense the steam in furnace 10.
- the material of construction of the furnace is not standard. Specialty materials such as tungsten or tantalum may be used.
- the temperature rise should occur in a short period of time.
- the hydrogen furnace may be of the double-radiant-section box-type as pictured in FIG. 19.5, p. 681, of D. Q. Kern, Process Heat Transfer, McGraw-Hill Book Co., New York (1950).
- the furnace may use tantalum (Ta) tubing ($170/lb.) because of its high melting point, 3269 K.
- FIG. 2 a schematic diagram showing another embodiment of the method of this invention is provided.
- natural gas is heated in high-temperature reactor 20 by means of electrical power that is produced by utilization of hydrogen in electrical power generator 21.
- the electrical power may be produced by fuel cells powered by hydrogen or by a combined cycle gas turbine driving electrical generators, for example. Water is also produced. Investment costs for fuel cell production of electrical power are high at present, but may be reduced by improved technology in the future.
- Combined cycle gas turbines are well known and at present produce electrical power at significantly lower capital costs per kW (approximately $385 per kW) than the capital costs of fuel cells (estimated at $3,000 per kW). In either case, the electrical power is used to increase temperature of the natural gas stream entering high-temperature reactor 20.
- the high temperature may be produced from the electrical power by an electric arc or silent discharge between electrodes, using methods well known in the art.
- the high temperature may be produced by resistance heating of carbon or other materials.
- a plasma may be formed in the natural gas stream using a "Plasmatron” such as sold by Praxair, Thermal Spray Systems, N670 Communication Drive, Appleton, Wis. 54915. Plasma temperatures are higher than the preferred temperature range for the gas reactions of this invention, so a more energy-efficient process may be achieved without bringing the natural gas to plasma temperature. The extra temperature produces extra components in the product stream that require a great deal more energy and would make the process not be as energy efficient. Quench vessel 22, separator 23, catalytic reactor 24 and preheater 25 serve functions described above relative to FIG. 1.
- the reactive hydrocarbon stream coming from the hydrogen furnace or the electrically-heated reactor can be essentially one part acetylene (with small amounts of ethylene and other hydrocarbons) to three parts methane. This is the preferred feedstock for the catalytic reactor-separator 13 of FIG. 1 or the catalytic reactor-separator 24 of FIG. 2.
- the catalytic reactor may include recycle.
- the liquefaction reaction and subsequent steps can be the same for the processes depicted in FIGS. 1 and 2.
- the principal liquefaction reactions in the catalytic reactor are as follows:
- This reaction must be catalyzed to suppress the reaction of acetylene to benzene and to enhance the conversion to pentane and higher compounds, which are preferred for the method of this invention.
- the liquefaction reactor shown in FIGS. 1 and 2, 13 and 24 respectively should produce predominantly pentane, but may also produce butane, hexane, heptane and some aromatic and cyclic compounds.
- the vapor pressure of pentane is about 1 bar at 40° C. Thus, it can be transported via truck or ship. Heavier hydrocarbons such as crude oil may be added to the produced liquid to reduce vapor pressure of a liquid to be transported.
- the reaction to produce pentane is thermodynamically favorable.
- the equilibrium thermodynamics for the reactions of acetylene and ethylene with methane are more favorable at low to moderate temperatures (300-1000 K).
- alkanes of ethane and higher can be converted to higher molecular weight hydrocarbons using the zeolite catalyst H-ZSM-5.
- the acidity of H-ZSM-5 can be varied by altering the silica to alumina ratio in the catalyst (typical ratios range from 30 to 30,000) to make possible alkylation of acetylene with methane, thus forming higher molecular weight hydrocarbons, predominantly pentane.
- Other alkylation catalysts are known in the chemical industry.
- the reaction of acetylene and ethylene to benzene is suppressed and the reaction of these reactive hydrocarbons with methane is enhanced.
- Steam may be introduced into the reactor to achieve the desired conversion results.
- the preferred reactor conditions are temperature in the range from about 300 to about 800 k and pressure in the range from about 2 to about 30 bar.
- a cooling step and a separation step may be considered a part of the catalytic reactor of FIGS. 1 and 2 (13 and 24, respectively). Cooling of the stream after the reaction may be necessary, depending upon the method of final separation and the optimum conditions for that separation. If the separation is simply a gas-liquid or flash separation, cooling may be necessary. Distillation, adsorption or absorption separation processes, including pressure-swing adsorption and membrane separation, may be used for the final separation. Any known hydrocarbon liquid-gas separation processes may be used for the final separation step, which is considered a part of the catalytic reactor. Liquid hydrocarbon then goes to storage or transport facilities and hydrogen is transported to the furnace shown is FIG. 1 or the electrical generation method discussed above in connection with FIG. 2.
- FIG. 3 shows a plot of number of moles of each species versus temperature for a pressure of 10 bars, starting with one mole of methane. Note that at a temperature in the range of 2500 K very little methane is present and that at about 1700 K the ratio of acetylene and methane is approximately correct for the liquefaction reactor (3 moles methane per mole acetylene). A near maximum amount of molecular hydrogen is present at 2500 K; this amount drops off at higher temperatures because of the formation of atomic hydrogen, as indicated by the curve near the bottom of the figure. The amount of ethylene present increases and is a maximum at about 1500 K.
- Tables 1, 2 and 3 show the calculations of the mole fractions and number of moles of each reactant when two moles of methane are at equilibrium at temperatures of 2500 K, 2000 K and 3000 K, respectively. These calculations are shown at pressures of 1 bar, 10 bars and 50 bars. Also shown are the change in enthalpy during the reaction of two moles and the change in enthalpy ( ⁇ H) per mole of methane. These calculations were performed using the method described in chemical engineering thermodynamics textbooks, such as Introduction to Chemical Engineering Thermodynamics by Smith, Van Ness and Abbott (McGraw-Hill). A notation at the bottom of Table 1 indicates that the moles of hydrogen produced may then be burned with oxygen to produce 850 kJ at 100% thermal efficiency. Thus, little or no consumption of natural gas for fuel will be necessary.
- the method of this invention is used in a large plant for converting natural gas to liquid.
- a 2-gigawatt electrical power plant is located remotely from a large natural gas field and costs of a pipeline connecting the two prevent development of the natural gas field.
- Equipment for the process shown in FIG. 1 is provided near the location of the gas field.
- the power plant requires about 5 billion BTU per day of fuel. This amount of fuel requires a gas-to-liquid plant treating about 6,000 standard cubic feet per second of natural gas, or 520 million standard cubic feet per day.
- the plant produces about 3.6 million GPD of liquid hydrocarbons that can be sent by truck, train or ship to the power plant, and about 2.25 million GPD of water, enough to supply a town with a population of 30,000, or, alternatively, to irrigate about 2,500 acres of desert for crop production.
- the plant requiring only a furnace for burning the hydrogen and widely available equipment for the quenching, liquefaction and separation steps, requires far less capital investment than a plant based upon the F-T process. In addition, little or no energy costs are associated with operation of the plant because the hydrogen produced in the process provides sufficient energy in the furnace.
- a remote natural gas well produces natural gas at a rate of 10 million standard cubic feet per day.
- the gas from this well is liquefied for truck transport to a market.
- the process of FIG. 1 is applied using trailer-mounted vessels to produce 1,725 BPD of liquid hydrocarbons.
- the capital cost of the equipment is about $20 million, or about $11,600 per BPD capacity.
- the plant is moved to other wells when production from the initial well declines to an uneconomic rate.
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Abstract
Description
2CH.sub.4 →C.sub.2 H.sub.2 +3H.sub.2,
4CH.sub.4 →2C.sub.2 H.sub.4 +4H.sub.2.
3CH.sub.4 +C.sub.2 H.sub.2 =C.sub.5 H.sub.12 +H.sub.2,
CH.sub.4 +2C.sub.2 H.sub.4 =C.sub.5 H.sub.12.
TABLE 1 ______________________________________ Energy Required by the High Temperature Reactor at 2,500 K. 2CH4 = iC2H2 + jC2H4 + kH2 +IH 1bar 10 bar 50 bar Compound x n x n x n ______________________________________ CH4 (g) 0.00046 0.00157 0.00457 0.01567 0.02187 0.07176 C2H2 (g) 0.14601 0.49890 0.14261 0.48902 0.13711 0.44991 C2H4 (g) 0.00009 0.00032 0.00092 0.00314 0.00433 0.01421 H2 (g) 0.83045 1.82496 0.84452 1.81185 0.83340 1.68762 H (g) 0.02299 0.05053 0.00739 0.01586 0.00329 0.00666 ΔH (kJ) 648 637 622 ΔH (kJ/mol Cl) 324 318 311 ______________________________________ Note: we have 850 kJ available from the hydrogen produced in the process
TABLE 2 ______________________________________ Energy Required by the High Temperature Reactor at 2,000 K. 2CH4 = iC2H2 + jC2H4 + kH2 +IH 1bar 10 bar 50 bar Compound x n x n x n ______________________________________ CH4 (g) 0.00500 0.01721 0.04506 0.13980 0.16146 0.38846 C2H2 (g) 0.14176 0.48847 0.13111 0.40675 0.10165 0.24458 C2H4 (g) 0.00085 0.00293 0.00753 0.02335 0.02543 0.06119 H2 (g) 0.85083 1.81628 0.81581 1.54213 0.71125 0.99890 H (g) 0.00157 0.00335 0.00049 0.00920 0.00020 0.00029 ΔH (kJ) 559 532 473 ΔH (kJ/mol Cl) 279 266 237 ______________________________________ Note: we have 850 kJ available from the hydrogen produced in the process
TABLE 3 ______________________________________ Energy Required by the High Temperature Reactor at 3,000 K. 2CH4 = iC2H2 + jC2H4 + kH2 +IH 1bar 10 bar 50 bar Compound x n x n x n ______________________________________ CH4 (g) 0.00001 0.00027 0.00092 0.00308 0.00461 0.01562 C2H2 (g) 0.16041 0.49980 0.14874 0.49775 0.14428 0.48866 C2H4 (g) 0.00009 0.00007 0.00021 0.00072 0.00104 0.00353 H2 (g) 0.71641 1.69345 0.80699 1.79569 0.83026 1.79600 H (g) 0.12307 0.29091 0.04314 0.00960 0.01980 0.04284 ΔH (kJ) 801 736 741 ΔH (kJ/mol Cl) 401 368 370 ______________________________________ Note: we have 850 kJ available from the hydrogen produced in the process
Claims (54)
Priority Applications (14)
Application Number | Priority Date | Filing Date | Title |
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US09/199,502 US6130260A (en) | 1998-11-25 | 1998-11-25 | Method for converting natural gas to liquid hydrocarbons |
DE69912312T DE69912312T2 (en) | 1998-11-25 | 1999-11-23 | METHOD FOR CONVERTING NATURAL GAS IN LIQUID HYDROCARBONS |
AU23490/00A AU769580B2 (en) | 1998-11-25 | 1999-11-23 | Method for converting natural gas to liquid hydrocarons |
ES99967151T ES2212665T3 (en) | 1998-11-25 | 1999-11-23 | PROCEDURE TO CONVERT NATURAL GAS IN LIQUID HYDROCARBONS. |
CA002352243A CA2352243C (en) | 1998-11-25 | 1999-11-23 | Method for converting natural gas to liquid hydrocarbons |
BRPI9915634-2A BR9915634B1 (en) | 1998-11-25 | 1999-11-23 | method for converting natural gas into liquid hydrocarbons. |
MXPA01005265A MXPA01005265A (en) | 1998-11-25 | 1999-11-23 | Method for converting natural gas to liquid hydrocarons. |
AT99967151T ATE252528T1 (en) | 1998-11-25 | 1999-11-23 | METHOD FOR CONVERTING NATURAL GAS INTO LIQUID HYDROCARBONS |
IDW00200101389A ID29855A (en) | 1998-11-25 | 1999-11-23 | METHOD FOR CONVERTING NATURAL GAS TO LIQUID HYDROCARBONS |
PCT/US1999/028005 WO2000031004A1 (en) | 1998-11-25 | 1999-11-23 | Method for converting natural gas to liquid hydrocarons |
EP99967151A EP1140738B1 (en) | 1998-11-25 | 1999-11-23 | Method for converting natural gas to liquid hydrocarons |
US09/574,510 US6323247B1 (en) | 1998-11-25 | 2000-05-19 | Method for converting natural gas to liquid hydrocarbons |
US09/803,122 US6602920B2 (en) | 1998-11-25 | 2001-03-09 | Method for converting natural gas to liquid hydrocarbons |
US10/611,564 US7119240B2 (en) | 1998-11-25 | 2003-07-01 | Method for converting natural gas to olefins |
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US09/199,502 US6130260A (en) | 1998-11-25 | 1998-11-25 | Method for converting natural gas to liquid hydrocarbons |
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US09/574,510 Expired - Lifetime US6323247B1 (en) | 1998-11-25 | 2000-05-19 | Method for converting natural gas to liquid hydrocarbons |
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EP (1) | EP1140738B1 (en) |
AT (1) | ATE252528T1 (en) |
AU (1) | AU769580B2 (en) |
BR (1) | BR9915634B1 (en) |
CA (1) | CA2352243C (en) |
DE (1) | DE69912312T2 (en) |
ES (1) | ES2212665T3 (en) |
ID (1) | ID29855A (en) |
MX (1) | MXPA01005265A (en) |
WO (1) | WO2000031004A1 (en) |
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AU769580B2 (en) | 2004-01-29 |
EP1140738B1 (en) | 2003-10-22 |
ES2212665T3 (en) | 2004-07-16 |
BR9915634B1 (en) | 2011-06-28 |
ATE252528T1 (en) | 2003-11-15 |
MXPA01005265A (en) | 2004-03-10 |
CA2352243C (en) | 2008-05-27 |
ID29855A (en) | 2001-10-18 |
US6323247B1 (en) | 2001-11-27 |
EP1140738A1 (en) | 2001-10-10 |
AU2349000A (en) | 2000-06-13 |
DE69912312D1 (en) | 2003-11-27 |
DE69912312T2 (en) | 2004-07-29 |
WO2000031004A1 (en) | 2000-06-02 |
BR9915634A (en) | 2001-11-06 |
CA2352243A1 (en) | 2000-06-02 |
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